The bond dissociation energies of SO3—X– (X = F, Cl, Br, and I)

2005 ◽  
Vol 83 (11) ◽  
pp. 2013-2019 ◽  
Author(s):  
Changtong Hao ◽  
Thomas M Gilbert ◽  
Lee S Sunderlin
Keyword(s):  
Gas Phase ◽  
Lewis Acids ◽  
Basis Sets ◽  
Collision Induced Dissociation ◽  
Bond Dissociation Energies ◽  
Flowing Afterglow ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Upper Limit ◽  
Bond Strengths

The gas-phase strengths of the SO3—X- bonds (X = Cl, Br, and I) have been determined to be 222 ± 13, 179 ± 11, and 161 ± 9 kJ/mol, respectively, by measuring thresholds for collision-induced dissociation in a flowing afterglow-tandem mass spectrometer. An upper limit of D(SO3—F–) ≤ 488 ± 19 kJ/mol was also determined. The periodic trends in the halide affinities of SO3 closely parallel those for SO2 and other Lewis acids. Bond strengths computed using the B3LYP, MP2, QCISD(T), and other models with several basis sets are generally lower than experiment.Key words: bond dissociation energies, computational chemistry, Lewis acids, superacids, halide affinities.

scholarly journals Bond Dissociation Energies in the Gas Phase for Large Molecular Ions by Threshold Collision-Induced Dissociation Experiments: Stretching the Limits

2020 ◽  
Vol 124 (42) ◽  
pp. 8692-8707
Author(s):  
Marek Bot ◽  
Vladimir Gorbachev ◽  
Alexandra Tsybizova ◽  
Peter Chen
Keyword(s):  
Gas Phase ◽  
Molecular Ions ◽  
Collision Induced Dissociation ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies

Bond dissociation energies in glycine, alanine, and dipeptide deprotonated anions for use in analyzing collision-induced dissociation processes

2018 ◽  
Vol 429 ◽  
pp. 212-226 ◽  
Author(s):  
Ashley S. McNeill ◽  
Can Cui ◽  
Sean R. Miller ◽  
Michele L. Stover ◽  
Maranda Burns ◽  
...  
Keyword(s):  
Collision Induced Dissociation ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies

Thermochemistry of Elementary Actinide Sulfide Molecules: A Gas-Phase Study of Curium Sulfide

2010 ◽  
Vol 1264 ◽  
Author(s):  
Cláudia C. L. Pereira ◽  
Joaquim Marçalo ◽  
John K. Gibson
Keyword(s):  
Gas Phase ◽  
Bond Dissociation Energies ◽  
Gas Phase Reactions ◽  
General Applicability ◽  
Molecular Systems ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Phase Study ◽  
Fundamental Understanding ◽  
Actinide Ions

AbstractExperiments to explore the reactivity and thermochemistry of elementary transuranium sulfide molecules have been initiated to expand the basis for a fundamental understanding of actinide bonding, and to enable the development of advanced theoretical methodologies which will be of general applicability to more complex molecular systems. Bimolecular gas-phase reactions between transuranium actinide ions and neutral reagents are employed to obtain thermochemical information. The initial actinide sulfide studies have focused on obtaining the 298 K bond dissociation energy for the CmS+ ion, D[Cm+-S] = 475±37 kJ mol-1; from this result and an estimate of IE[CmS] ≈ IE[CmO] + 0.5 eV, we obtain D[Cm-S] = 563±64 kJ mol-1. The bond dissociation energies, D[Cm+-S] and D[Cm-S] are approximately 200 kJ mol-1 and 150 kJ mol-1 lower than for the corresponding oxides, CmO+ and CmO. The nature of the bonding in the CmS+ ion appears to be generally similar to that in other oxophilic metal sulfides. Comparisons with previous bond dissociation energies reported for ThS and US may suggest a difference in the An-S bonds for these early actinide sulfides as compared with CmS.

THEORETICAL STUDIES ON BOND DISSOCIATION ENERGIES FOR SOME THIOL COMPOUNDS BY DENSITRY FUNCTIONAL THEORY AND CBS-Q METHOD

2008 ◽  
Vol 07 (05) ◽  
pp. 943-951 ◽  
Author(s):  
XIAO-HONG LI ◽  
ZHENG-XIN TANG ◽  
ABRAHAM F. JALBOUT ◽  
XIAN-ZHOU ZHANG ◽  
XIN-LU CHENG
Keyword(s):  
Density Functional ◽  
Computational Cost ◽  
Basis Set ◽  
Basis Sets ◽  
Q Method ◽  
Bond Dissociation Energies ◽  
Functional Theory ◽  
Thiol Compounds ◽  
Bond Dissociation ◽  
Dissociation Energies

Quantum chemical calculations are used to estimate the bond dissociation energies (BDEs) for 15 thiol compounds. These compounds are studied by employing the hybrid density functional theory (B3LYP, B3PW91, B3P86, PBE0) methods and the complete basis set (CBS-Q) method together with 6-311G** basis set. It is demonstrated that B3P86 and CBS-Q methods are accurate for computing the reliable BDEs for thiol compounds. In order to test whether the non-local BLYP method suggested by Fu et al.19 is general for our study and whether B3P86 method has a low basis set sensitivity, the BDEs for seven thiol compounds are also calculated using BLYP/6-31+G* and B3P86 method with 6-31+G*, 6-31+G**, and 6-311+G** basis sets for comparison. The obtained results are compared with the available experimental results. It is noted that B3P86 method is not sensitive to the basis set. Considering the inevitable computational cost of CBS-Q method and the reliability of the B3P86 calculations, B3P86 method with a moderate or a larger basis set may be more suitable to calculate the BDEs of the C–SH bond for thiol compounds.

Experimental and computational studies of deuterated ethanols: gas-phase acidities, electron affinities and bond dissociation energies

1993 ◽  
Vol 123 (3) ◽  
pp. 171-185 ◽  
Author(s):  
Thuy Thanh Dang ◽  
Edwin L. Motell ◽  
Michael J. Travers ◽  
Eileen P. Clifford ◽  
G. Barney Ellison ◽  
...  
Keyword(s):  
Gas Phase ◽  
Computational Studies ◽  
Bond Dissociation Energies ◽  
Electron Affinities ◽  
Bond Dissociation ◽  
Dissociation Energies

Acidities and homolytic bond dissociation energies of the αC—H bonds in ketones in DMSO

1990 ◽  
Vol 68 (10) ◽  
pp. 1714-1718 ◽  
Author(s):  
Frederick G. Bordwell ◽  
John A. Harrelson Jr
Keyword(s):  
Gas Phase ◽  
Radical Cations ◽  
Bond Dissociation Energies ◽  
Bond Dissociation ◽  
Dissociation Energies ◽  
Oxidation Potentials ◽  
Stabilization Energies ◽  
Conjugate Bases

Equilibrium acidities in DMSO are reported for nine cycloalkanones, acetone, acetophenone, and 19 of their α-substituted derivatives. Oxidation potentials in DMSO for the conjugate bases of most of these ketones are also reported. Combination of these EOX(A−) and pKHA values gives estimates of the homolytic bond dissociation energies (BDEs) of the acidic C—H bonds in the ketones. The ΔBDEs, relative to the BDE of CH3-H, or a parent ketone, provide a measure of the radical stabilization energies (RSEs) of the corresponding radicals. The effects of successive α-Me and α-Ph substitutions on RSEs, relative to those of CH3COCH2-H or PhCOCH2-H, are similar to those reported in the gas phase for methane. The RSE for the MeĊHCOPh radical, relative to CH3• is 17 kcal/mol, which is smaller than the sum of the RSEs of the MeCH2• and PhCOCH2• radicals relative to CH3• (7 + 12 = 19), contrary to the prediction of the captodative postulate. When G in PhCOCH2G is PhCO, CH3CO, or CN the ΔBDEs (relative to PhCOCH2-H) are 0, 1, and 3 respectively; for MeCOCH2SO2Ph, PhCOCH2SO2Ph, and PhCOCH2NMe3+ the ΔBDEs are −5, −2, and −4, respectively. The BDEs in C5, C6, C7, C8, C10, and C12 cycloalkanones are within ±2.5 kcal/mol of that of 3-pentanone. Acetophenones bearing meta or para substituents all have BDEs of 93-94 kcal/mol. Ketone radical cations, [RCOR′]+•, appear to be superacids with estimated [Formula: see text] values below −25. Keywords: acidities, bond dissociation energies, ketones.

ChemInform Abstract: Experimental Studies of Allene, Methylacetylene, and the Propargyl Radical: Bond Dissociation Energies, Gas-Phase Acidities, and Ion- Molecule Chemistry.

ChemInform ◽  
2010 ◽  
Vol 26 (43) ◽  
pp. no-no
Author(s):  
M. S. ROBINSON ◽  
M. L. POLAK ◽  
V. M. BIERBAUM ◽  
C. H. DEPUY ◽  
W. C. LINEBERGER
Keyword(s):  
Gas Phase ◽  
Experimental Studies ◽  
Bond Dissociation Energies ◽  
Propargyl Radical ◽  
Bond Dissociation ◽  
Dissociation Energies
Sign in / Sign up

Export Citation Format

Share Document